Dyeing of polyester fibers with com-



United States Patent 3,103,403 DYElNG 0F POLYESTER FIBERS WITH COM- POUNDS OF THE NAPHTHOYLENE -ARYL- IMINAZOLE SERIES David Crawford Eaton and Francis Irving, Manchester, England, assignors to Imperial Chemical Industries Limited, London, England, a corporation of Great Britain No Drawing. Filed Feb. 6, 1961, Ser. No. 87,092 Claims priority,'application Great Britain Feb. 17, 1960' 5 Claims. (Cl. 855) This invention relates to a colouration process and more particularly it relates to a colouration process for artificial polymeric materials. a

United Kingdom patent specification No. 789,310 describes and claims a process tor the production of dyestuffs of the naphtlmoylene-aryl-iminazole series and f the naphthaloperinone series which comprises treating textile fibres with an aqueous composition comprising an organic oarboxylic acid having at least 2 carboxylic acid groups in peri position to each other, or a nuclear substitution product thereof, and an osdiamine or peri diamine, or a substitution product thereof, and a condensing agent which is an acid or an ammonium salt thereof, and subjecting the fibres thus treated to a' heat treatment.

We have now discovered that certain compounds of the naphthoylene-aryl-iminazole series may be used directly for the colouration of artificial polymeric materials, especially polystyrene and polyesters such as polyethylene terephthalate', and that the colours produced in eucilh materials have excellent fastness to heat and to lg t. i

According to our invention therefore we provide a process for the colouration of an artificial polymeric material selected from polystyrene, and polyesters which comprises treating said material with a colouring matter which is devoid of sulphonic acid and carboxylic acid groups and is of the formula wherein R represents an o or per-i-arylene radical and forexample nitro, cyano, halogeno such-as chloro and bromo, allcoxy such as methoxy and butoxy, alkyl such as methyl and butyl and substituted alkyl, for example allroxyal'kyl such as w-methoxypropyl. As a further ex- Patented Sept. 10, 1963 7 As examplesof alkyl, aralkyl and aryl radicals represented by R there may be mentioned methyl, ethyl, propyl, benzyl, phenyl, a-naphthyl and p-naphthyl. Aralkyl and aryl radicals represented by R may carry substituents, for example halogeno such as chloro and bromo, nitro, alkyl such as methyl, and alkoxy such as methoxy. As examples of substituents which may be present in a substituted alkyl group represented by R there may be mentioned halogeno such as chloro and brorno, alkoxy such as methoxy, alkylamino such as methylamino, and arylaminosuch as phenylamino'.

The process of our invention may be used for colouring plastic materials by conventional means. For example the colouring matter, preferably in finely divided form may be mixed with chips of the artificial polymeric material and the mixture may be rinsed and masticated (or trit-urated on a hot roll mill), cooled and granulated by suitable means to give a coloured moulding powder. The moulding powder may then be used in the manufacture of shaped articles which are coloured in yellow to violet shades of excellent dastness to light.

Preferably however the process of our invention may be used as a means of colouring textile materials comprising fibres cf the artificial polymeric material, for example polyester tibres, especially polyethylene terephthalate fibres. For this purpose the colouring matter is advantageously first dispersed in water by grinding or milling with a dispersing agent such as disodium dinaphthylmethane disulphonate. Colouration of the textile material may then be carried out with a fine aqueous suspension of the colouring matter in the presence of a carrier (for example p-hydroxydiphenyl) at or near the boiling point, or without the addition [of a carrier at a temperature above =100" C. under superatmospheric pressure. The textile materials are coloured in yellow to violet shades of very good fastness to light. We find that the fastest dyeings are obtained by the use of the colouring matters wherein -R represents an -o-phenylene or a ample of a peri-arylene radical represented by R there i may be mentioned the divalent radical of formula substituted 'o-phenyl'ene radical, and those wherein R represents a phenyl or a substituted phenyl radical.

Colouring matters suitable for use the process of our invention may be obtained by condensation of a dicarboxylic acid of the formula H000 OOOH For other means; Mixtures obtained in this way may,

however, advantageously be used in the process of the invention. I

The invention is illustrated but not limited by the following examples in which the parts are by weight:

Example 1 parts'odf polyethylene terephthalate staple yarn (100 parts) is dyed for 30 minutes at C. under superatmcspheric pressure with a fine dispersion of 0.3 part of a mixture of 3- and 4-benzo-ylnaphthoylenebenzimiazole in 3000 parts of water containing a little: disodium dinaphthylmethaneadi-fissulphonate. The yarnv is rinsed well and treated for 15 minutes at 55 C. with a solution of 7 parts of sodium hydroxide and 2 parts of sodium hydrosulphitein 1000 parts of water. After rinsing the yarn, optionally in the presence of a detergent, a clear greenish-yellow dyeing is obtained with very good fastness to light and to dry heat.

The mixture 7 of 3- and 4-benzoylnaphthoylenebenziminazole may be obtained by heating a mixture of 6 parts of benzoylnaphthalic acid or its anhydride, 3 parts of o-phenylenediamine and 20 parts oi glacial acetic acid under reflux :Eor 1 hour. On pouring the reaction mix ture into 1 parts water, the product isobtained as a fine yellow prem'pitate which is isolated by filtration, washing and drying.

If the said mixture of benzoylnaphthoylenebenziminazoles is crystallised twice from n-butanol a highly crystalline product, of melting point 188 C. is obtained. When dispersed in water it dyes polyethylene terephthalate fibre in clear greenish-yellow shades of very good fastness to heat and light.

Example 2 Polyethylene terephthalate fabric is dyed with a mixture of benzoylnaphthoylene-chloroben'ziminazoles by the dyeing procedure described in Example 1. A clear greenish-yellow dyeing is obtained having very good fastness to light and to dry heat.

The mixture of benzoylnaphthoylene chloroben-ziminazoles may be obtained by reacting 7.7 parts of 4-benzoylnaphthalic acid, 5.5 parts of 4-chloro-1z2-diaminobenzene in 20 parts of glacial acetic acid according to the conditions described in Example 1.

If the said mixture of lbenzoylnaphthoylene chlorobenziminazoles is crystallised twice from n-butanol a highly crystalline product, of melting point 194-8 C. is obtained. When dispersed in water this also dyes polyethylene terephthalate in clear greenish-yellow shades having very good fastness to light and to dry heat.

Example 3 Example 4 0.2 part of the dyestufi mixture used in Example 3 is mixed with 100 parts of polystyrene which is then triturated on a hot roll mill. The mixture is then cooled and vgranulated and there is obtained a polystyrene moulding powder which may be converted to a fluorescent yellow moulding by heating for 15 minutes at 240 C. and then cooling. The moulding has very good light fastness and excellent heat stability.

Example 5 Polyethylene terephthalate fabric is dyed with a mixture of 3- and 4-acetylnaphthoylenebenziminazole by the dyeing procedure described in Example 1. A bright yellow dyeing of very good fastness to light is obtained. 1

The dyestuff mixture used in this example may be prepared by reacting 2.4 parts of 4-acetylnaphthalic acid or anhydride and 1.62 parts of lz2-diaminobenzene in 15 parts of glacial acetic acid according to the conditions described in Example 1.

Example 6 Polyethylene terephthalate fabric is dyed with a mixture of acetylnaphthoylene-chlorobenziminazoles by the dyeing procedure described in Example 1, whereby a bright yellow dyeing of very good light fastness is obtained. The dyestufi mixture used in this example may be prepared by reacting 2.4 parts of 4-iacetylnaphthalic acid or anhydride and 2 parts of 4-chloro-lc2-diaminobenzene in 15 parts of glacial acetic acid according to the conditions described in Example 1.

Example 7 Polyethylene terephthalate fabric is dyed with a mixture of benzoylnaphthoylene-cyanobenziminazoles by the dyeing procedure described in Example 1, whereby a greenish yellow dyeing of very good fastness to light and dry heat is obtained. The 'dyestufi mixture used in this example may be prepared by reacting 2 parts of 4-benzoylnaphthalic acid or anhydride and 1 part of 4-cyano- 1:2-diaminobenzene in 20 parts of glacial acetic acid according to the conditions described in Example 1.

Example 8 Example 9 Polyethylene terephthalate fabric is dyed with a mixture of acetylnaphthaloperinones obtained as described below, by the dyeing procedure described in Example 1 whereby *a dyeing of excellent fastness to dry heat is obtained. The dyestuif used in this example may be prepared by reacting 3 parts of 4-acetylnaphthalic acid or anhydride and 2.2 parts of 1:8-diaminonaphthalene in 60 parts of, glacial acetic acid according to the conditions described in Example 1.

1 Example 10 Polyethylene terephthalate fabric is dyed with 13. mixture of n-butyrylnaphthoylene 'benz-iminazoles by the dyeing procedure described in Example 1 whereby a clear yellow dyeing of very good fastness to light is obtained. The dyestuff mixture used in this example may be prepared by reacting 2.82 parts of 4-n-butyrylnaphthalic acid or anhydride and 1.3 parts of 1:2 diaminobenzene according to the conditions described in Example 1. 4-n-butyrylnaphthalic acid or anhydride may be obtained by reacting acenaphthene with 1 molecular equivalent of n-butyrylchloride and oxidising the resultant 5-n-butyrylacenaphthene according to the method described by Graebe in Liebigs Annalen, volume 327, page 94.

Example 11 Polyethylene terephthalate fabric is dyed with a mixture of nbutyrylnaphthoylenebhlorbenziminazoles byv the dyeing procedure described in Example 1 whereby a clear yellow dyeing of very good fastness to light is obtained. The dyestutf mixture used in this example may be prepared by reacting 2.82 parts of 4-n-butyrylnaphthalic acid or anhydride and 1.7 parts of 4-ch1oro-1:2-diaminobenzene in 20 parts of glacial acetic acid according to the conditions described in Example 1.

Example 12 Polyethylene terephthalate fabric is dyedwith a mix Example 13 Polyethylene terephthalate fabric is dyed with a mixture of n-butyrylnaphthoylene-methyl-benzliminazoles by the dyeing procedure described in Example 1 whereby a yellow dyein'g of very good fastness to light is obtained. The dyestuff mixture used in this example may be prepared by reacting 1.41 parts of 4-n -butyry1naphthalic acid or 'anhydride and 0.75 part of 1-methyl-324-diamindbenzene in parts of glacial acetic acid according to the conditions described in Example 1.

Example 14 Polyethylene terephthalate 'fabric is dyed with a mix:

ture of benzoylnaphthoylene-methoxybenziminazolesvby the dyeing procedure described in Example 1 whereby a strong yellow dyeing of very good fastness to light and dry heat is obtained. The dyestufi mixture rusedgin this example may be prepared by reacting 3.02 parts of 4- 1 benzoylnaphthalic acid or anhydride and 2.07parts of 4-methoxy-l:2 diaminobenzene in parts of glacial acetic acid according to the conditions described in Example 1. If desired the dyestulf may be purified by dissolving in hot n-butanol and cooling 'lthe solution and filtering off the solid which separates.

I Example'15 4 Polyethylene terephthalate fibre is dyed 'With a. mixture of acetylnaphtheylene-methoxy-benziminazoles by the dyeing procedure described in Example 1, whereby a strongyellow dyeing of very (good fastness to light is obtained. =The dyestuif mixture used in thisexample may be prepared by reacting 2 parts-of 4 acetylnaphthalic acid or anhydride and 1.4 parts of 4-methoxy-1:2-diaminobenzene in 20 parts of glacial acetic acid according to the conditions described inExample 1.

Example 16 Polyethylene terephthalate fabric is dyed with ture of benzoylnaphthoylenenitrobenzin'iinazoles by (the dyeing procedure described in Example 1 whereby a greenish yellow dyeing of very good fastness to dry heat is obtained. The dyestufi mixture used in this example a mix- 6 or 4-p-chlorbenzoylnaphthalic.acid' or arihydride and 1.3 parts or 4-n-butyl-.1:Z-diaminobenzene lILZO pants ocf glacial acetic acid according to the conditions described in Example 1. 4-p-chlorobenzoylnaphthalic acid or anhydride may be obtained by reacting acenaphthene with 1; lm-olecular equivalent of p-chlorbenzoylchloride and oxidising the resultant 5 p-chlorbenzoylacenaphthene by the method described by Graebe' in Liebigs Annalen,

volume 327, page 94.

3 Example 2 0 b Example 21 1 a Polyethylene terephthalate. fabric is dyed w'th a the dyeing procedure described in'Example 1 whereby a yellow dyeing of very good fastne'ss to light and dry heat is obtained. The -dycstufi tuned in this example may be prepared by reacting 2 parts of 4-'b-enzoylnaphthalic acid or anhydride .fillfilz parts of 4-n-bu toxy- 1:2-diarninobenzene in 20" parts bf glacial acetic acid according to the conditions described in Example 1. If

desired, the dyestuff may be purified by dissolvingin hotisoprop-anol, cooling and filtering off the solid which separates.

4-n-b:utoxy-1:Z-GiaminobenZene may be prepared by nitrating p-n-butoxyacetanilide withone molecular equivalent of nitric acid at about 0 I 0., hydnolysing the product so obtained with dilute mineral acid to give. 4-n-butoxy-2-nitroaniline, which may then'be reduced.-

to 4-n-butoxy-1:Z-diarninobenzene by a suitable reagent for ex-ample sodi-u'rn sulphide.

may be prepared by reacting 2.64 parts of .4 -benzoyl naphthalic acid 'or anhydride and 1.5 parts of 4-nitro-lz2- diaminobenzene in 25 parts Olf glacial acetic acid according to the conditions described in Example 1.

Example 17 Polyethylene terephthalate fabric is dyed with a mix- I ture of acetylnaphthoylene-nitrobenz-imi-nazoles by the dyeing procedure described in Example 1 whereby a clear yellow dyeing is obtained. The dyestufi mixture used in this example may be prepared by reacting 1.7 parts Clf 4-acetylnaphlthalic acid or anhydride and 1.25 parts of 4- nitro-l :Z-diaminobenzene in 20 parts of glacial acetic acid according to the conditions described in Example 1.

Example 18 Polyethylene terephthalate fabric is dyed with a mixture of benzoylnaphthoylene-n-butylbenzirninazoles by the dyeing procedure described in Example 1 whereby a yellow dyeing of very :good rfastness to light and dry heat is obtained. The dyestufi mixture used in this example may be prepared by reacting 2 parts of 4-benzoylnaphthalic acid or anhydride and 1.32 parts of 4-n-butyl- 1:2-diaminobenzene in 20 parts of glacial acetic acid according to the conditions described in Example 1.

Example 19 Polyethylene rterephthalate fabric is dyed with a mixture of p-chlorobenzoylnaphthoylene-n-butylbenziminazoles by the dyeing procedure described in Example 1 whereby a clear yellow dyeing of very good 'fastness to light and dry heat is obtained. The dyestuff mixture used in this example may be prepared by reacting 2 parts Example 22 Polyethylene terephthalate afiabric is dyed with a mixture of lacetylnaphthoylene-n butoxybenzirninazoles by the dyeing procedure described in Example 1, whereby a yellow dyeing of very good falstness to light is obtained. The mixture of acetylnaphthoylene-n-butoxybenziminazoles used in this example may be obtained by using 1.6 parts of 4-acetylnaphth=alic acid or anhydride in place of the 2 parts of 4-benzoylnap hthalic acid or anhydride used in the procedure described in Example 21.

Example 23 Polyethylene terepht-hala-te fabric is dyed with a mixtune of p-methoxybenzoylnaphthoylenebenzirninazoles by the dyeing procedure described in Example 1 whereby a yellow dyeing of 'very good :fastness to light :and dry heat is obtained. The dyestufi mixture used in this example may be prepared by reacting 3.32 parts of p methoxybenzoylnaphthalic acid or anhydride and 1.2 parts of 1:2-diaminobenzene in 20 parts of glacial acetic acid according to the conditions of Example 1. 4-p-methoxybenzoylnaphthalic acid or anhydride may be obtained by reacting acenaphthene with 1 molecular equivalent of pmethoxybenzoylchloride rand oxidising the product of the method described in Liebigs Annalen, volume 327, page 94.

Example 24 Polyethylene .terephthalate fabric is dyed with a mixture I of p-methoxybenzoylnaphthoylene-chlorbenziminazoles whereby a yellow dyeing of very good fastness to light and dry heat is obtained. The dyestulf mixture used in this example may be obtained by using 1.6 parts m'ixture of benzoylnaphthoylene-mbutoxy benzirninazoles of 4'-chlor0-1:2-diarninobenzene instead of 1.2 parts of 1:2-diarninohenzene in the procedure described in Example 23.

Example 25 Polyethylene :terephthaflate fabric is dyed with a mixture of ,8-etl'toxypropionylnaphthoylene-methytlbenziminazoles by the dyeing procedure described in Example 1, whereby a yellow dyeing of very good rfastness to light is obtained. The dyestufl mixture used in this example may be prepared by reacting 2.98 parts of 4-flethoxypnopionylnaph- 1 thalic acid or anhydride and 1. 34 parts of 4-methyl-lz2- diaminobenzene in 20 parts of glacial acetic acid accord-v ing to the conditions described in Example 1. 4-;3-ethoxypropi'onyhiaphthalic acid or anhydride may the prepared by reacting acenaphthene with 1 molecular equivalent of fi-ethoxypropilonylchloride and oxidising the product as described in Liebigs Annalen, volume 327, page 94.

Example 26 dyeing of very good fastness to dry heat is obtained. The

dyestufi mixture used in this Example may the prepared by reacting 298 parts of 4-fl-etlroxypropionylnaphthalic acid or amhydride with 1.74 parts of lz8-diaminonaphthalene in 60 parts of glacial acetic acid using the condensation conditions described in Example 1.

What we claim is; l 1. A process tor the coloration of a polyethylene terephthalate textile material which'comprises treating said material in an aqueous medium with a coloring matter free from sulphonic acid and carboxylic acid groups and having the. rformula:

wherein R is selected from the class consisting of 0- and peri-arylene radicals and the naphthalene nucleus A carries in one of the free eri-positions a radical of the formula R CO wherein R represents 'a member selected from the class consisting of alkyl, substituted alkyl, aralkyl and aryl radicals.

2. Process according to claim 1 wherein R represents a member selected {from the classconsisting of o-phenylene and substituted o-phenylene radicals.

'3. Process according to claim 1 wherein R represents a member selected from the class consisting-of phenyl and substituted phenyl radicals.

4. Process according to claim 1 wherein the textile material is treated with an aqueous dispersion of the 'dyestufi in the presence of a carrier at a temperature approximately the boiling point.

5. Process according to claim 1- wherein the textile material is treated with an aqueous dispersion of the dyestufi at a temperature above C.

References Cited in the file of this patent UNITED STATES PATENTS 7 2,955,902 Merian Oct. 11, 1960 V FOREIGN PATENTS I 789,310 Great Britain Jan. 15, 1958 

1. A PROCESS FOR THE COLORATION OF A POLYETHYLENE TEREPHTHALATE TEXTILE MATERIAL WHICH COMPRISES TREATING SAID MATERIAL IN AN AQUEOUS MEDIUM WITH A COLORING MATTER FREE FROM SULPHONIC ACID AND CARBOXYLIC ACID GROUPS AND HAVING THE FORMULA: 